Esters of epoxy alcohols with propenoic compounds



Patented 3, 1950 ESTERS OF EPOXY AL PROPEN OI George L. Borough. Nia

COHOLS WITH COMPOUNDS gara Falls, N. Y., assignor to E. I. du Pont de Nemours & Company, Wilmington, bet, a corporation of Delaware No Drawing. Application Au Serial 2 Claims.

This invention relates to new compositions of matter and more particularly to polymerizable compounds.

This invention has as an object a new class of 811st 17, 1945, No. 811,244

R is selected from thegroup consisting of hydrogen, halogen and monovalent organic radicals. Acids of this kind are the alpha, beta-ethylenically unsaturated monocarboxylic acids, e. g..

compounds which are useful for the produc i n 5 acrylic and methacrylic acids and the butenedioic f pl s ic nd polymeric materials and which are acids such as maleic and fumaric acids. In place also useful in their monomeric form for various of the above mentioned acids there can be used purposes. ur h r j s r ide in methods for their ester forming derivatives such as the anhyobtaining th se comp u ds. O her objects wi l drides,acy1 halides, esters, salts, and amides.

ppear hereinafter. 1 The invention is further illustrated by the 01:- Th above j s r a compl hed y reactlowing examples in which the parts are by weight. ing an esterifiable epoxy compound with an es- Emampl I terifiable propenoic compound under substanj tially neutral or alkaline conditions. More par- To a cold solution of 80 parts of sodium hydroxticularly the new compounds described herein are ide in 400 parts of water is slowly added 172 parts obtained by reacting an epoxy alcohol, for examof methacrylic acid. The resulting solution of 'plej 2,3-epoxy propanol, or its ester forming dethe sodium salt of methacrylic acid is cooledand rivative, for example, the halogen analogue with the pH adjusted to exactly 7.0. Then 5 parts of a propenoic acid or the ester forming derivative cuprous chloride is added, the mixture is'stirred of such acid. Still more particularly the new rapidly, and the dropwise addition of 180 parts compounds described herein are obtained by reof epichlorohydrin is carried out. A maximum acting an epoxy alcohol, or its ester forming detemperature rise of 15 C. occurs during the early rivative with an alpha, beta-ethylenically unsatportion of this addition. The mixture is stirred urated monocarboxylic acid or the ester forming for a total of 18 hours at ambient laboratory temderivative of such an acid. peratures and is then extracted four times with The esteriiication reaction as generally praca total of 450 parts of ether. The ether extract ticed is carried out by first charging a reaction is dried over anhydrous magnesium sulfate. The vessel with an alkali metal salt of the alpha, betaother is removed on a steam bath and the residue unsaturated carboxylic acid in a water medium fractionated under vacuum after adding 1 g. of present in sufficient amount toprovide asolution cuprous chloride. The following fractions are of the salt. For this purpose the acid is usually taken:

No. a. P. $32;

1 42 C./24 mm. to 50 C./l7 mm 76 Ugehanged epichlo'rohya 90-1145 one mm 2s 4. 102l17 0J2 mm 15 Very viscous 01'].

mixed in the reaction vessel with an aqueous solution of alkali hydroxide. To this solution is added an inhibitor, for example, cuprous chloride, to prevent polymerize The mixture is agitated at room temperature and epihalohydrin is added dropwise. When the reaction is complete, the contents of the reaction vessel are discharged and the reaction product is isolated by distillation or by other procedure.

The acids used in the practice of this invention are those of the general formula 'RrcH=CR'COOI-I wherein R is selected from the group consisting of hydrogen and monovalent organic radicals, and

tion of the product.

The production of polymers and of copolymers from epoxy esters obtained by the practiceof this invention is illustrated by the following examples.

Example II A mixture of 5 parts of the ester prepared as in flte in 200 parts of water.

Example I with 0.005 part of benzoin as a polymerization accelerator is exposed under a nitrogen atmosphere in a Pyrex vessel to the light of a Westinghouse 1-1-4 lamp at a distance of 6 inches. After one hour the mixture will no longer flow when the vessel is inverted. Exposure is continued for an additional 1'? hour period to give a slightly yellow, somewhat soft casting which can be hot pressed to a pliable sheet.

Example III A mixture of 153 parts of vinyl chloride, 17 parts of the ester prepared as in Example I, and 0.4 part of lauroyl peroxide is sealed in a glass container under nitrogen and heated at 35 C. for 9 days. The container is cooled and opened, and the unpolymerized portion poured off. The remaining polymerized product, after drying, amounts to 21 parts. Analysis indicates the presence of 42.7% copolymerized vinyl chloride. A hot pressed sheet of the product is substantially colorless and shows excellent resistance to discoloration on aging. On aging there is a gradual increase in hardness and a decrease in thermoplasticity and solubility so that after a 2-month period the product is no longer soluble in cyclohexa-none and broken pieces cannot be re-f-used by heating at 160 C. under 2,000 lbs/sq. in. pressure.

Example IV Mixtures of freshly distilled methyl-alphachloroaerylate with the 2,3-epoxypropyl methacrylate prepared as described in Example I, in the following proportions:

Per Cent Per Cent 2,3-

Sample Methyl Ghlrr Epoxypropyl roacrylate Methacrylate A 5 B Q0 10 C 100 0 Example V A mixture of 40 parts of acrylonitrile and 10 parts of 2,3-epoxypropyl methacrylate, prepared as described in Example I, is agitated at 40 C. under nitrogen with a solution of 0.5 part of ammonium persulfate and 0.1 part or sodium bisul- After 24.5 hours the precipitated polymer is filtered oil, washed with water and alcohol and dried at room temperature. The yield is 80 parts and analysis shows the 2,3-epoxypropyl methacrylate content to be The polymer is not soluble in dimethyl iormamide, a solvent for unmodified Dolyacrylonitrile.

A copolymer of acrylonitrile with 2,3-epoxy-- propyl methacrylate prepared by bulk polymerization in the presence of benzoyl peroxide is readily soluble in dimethyl formamide. A film of such copolymer on aging, particularly in an acidic environment, becomes insoluble and substantially infusible.

The epoxy esters of unsaturated acids described 1 herein can be made by various methods, such as by acid interchange, alcohol interchange, and reaction of the alcohol with the acid anhydride or halide.

Further examples of epoxy alcohols and esterforming derivatives thereof which are suitable in the practice of the present invention are epoxy oleyl alcohol, epoxy octadecanol, epoxydodecanol, 5,6-epoxyhexanol-2, 3,4-epoxy 2,2,4 trimethyl pentanol-3, beta-hydroxy ethyl ethylene oxide, 3- hydroxy-1,2-oxidocyclohexane, alpha hydroxymethyl-alpha-phenylethylene oxide, 3,4 dihydroxybenzyl ethylene oxide, and the like.

Examples of alpha, beta-ethylenically unsaturated acids or their ester-forming derivativeswhich can be used in place or metacrylic acid and acrylic acid are alpha-chloracrylic acid, alpha-phenyl acrylic acid, ammonium acrylates and methacrylates, crotonic acid, cinnamic acid, sorbic acid, beta-benzylacrylic acid, benzoylacrylic acid, beta-acetylacrylic acid, beta-furylacrylic acid, 4-ethyloctadien-2, 4-010 acid, hexadienoic acid, 5,9-dimethyldecatrien-2,4-8-olc acid, (A cyclohexadienyl)-propenoic acid, acrylyl chloride, methyl acrylate, ethyl methacrylate. Examples of butenedioic acids and their esters and salts are maleic and fumaric acids and their esters, suchas diethyl maleate, diethyl iumarate, etc., sodium, potassium, and ammonium, iumarates and maleates, etc.

In place of water such reaction media as allphatic or aromatic hydrocarbons, ethers, dioxan, and chlorinated hydrocarbons can be employed.

The reaction is best conducted with the esterifiable epoxy compound and the alpha, beta-unsaturated acid or its derivative in substantially mole proportions or under conditions providing for a slight deficiency of the esteriflable compound, thereby minimizing the iormation of side reaction products. The reaction temperatures can range from 0 C. to C. When it is desired to avoid polymerization, temperatures of 20 or lower and up to 30 are the most suitable.

The esters which are normally liquid are usually isolated and purified by fractional distillation. To minimize losses through polymerization of the ester, the fractional distillation is carried out in the presence of a polymerization inhibitor, such as copper chloride, copper acetate, copper resinate, copper propionate, p-phenylene diamine, hydroquinone, and the like.

Valuable products are obtained by polymerizing the epoxy esters either alone or with other polymerizable compounds and particularly with vinyl and vinylidene compounds. Further examples of such polymerizable compounds include the methyl, ethyl, and oetyl esters of acrylic, methacrylic and alpha-chloroacrylic acids, and the amides of these acids, e. g., acrylamide, methacrylamide, etc.; styrene, chlorostyrenes, vinyl acetate, methyl vinyl ketone, butadiene, isoprene, chloro-2-bu-' tadiene-1,3, fluoro-2-butadiene-1,3, 5-ethyl-2- vinylpyridine, 2-vinyl pyridine, vinyl furane, methacrylonitrile, acrylonitrile, methylene malonic esters, vinylidene chloride, vinyl fluoride, and fumaric and maleic esters.

The esters or this invention are useful as copolymeric stabilizers against heat degradation of normally unstable polymers, e. g., polyvinyl chloride, chlorinated polyethyienes, chlorinated rubber, and the like.

The polymers and copolymers described herein when hydrolyzed or subjected to conditions leading to scission or the ethylene oxide ring are susceptible of insolubilization.

As many apparently widely different embodiments or this invention may be made without departing from the spirit and to be understood that this invention is not thereby limited to the specific embodiments thereof. except as defined in the appended claims.

I claim:

1. 2,3epoxypropyl methacrylate.

2. A methacrylic acid ester of an epoxy alcohol in which there is a single epoxy oxygen which bridges adJacent carbon atoms.

GEORGE L. DOROUGH.

REFERENCES CITED The following references are or record in the flie of this patent:

cross-linking and consequent scope thereof, it is 5 6 UNITED STATES PA'I'ENTS Number Name Date 2,089,569 Orthner et a1 Aug. 10, 1937 2,129,666 Barrett et al Sept. 13, 1938 2,335,813 stein Nov, 30,- 1943 2,470,324 Staudinger et a1. May 17, 949

FOREIGN PATENTS Number Country Date 10 518,057 Great Britain Feb. 15, 1940 OTHER REFERENCES 

2. A METHACRYLIC ACID ESTER OF AN EPOXY ALCOHOL IN WHICH THERE IS A SINGLE EPOXY OXYGEN WHICH BRIDGES ADJACENT CARBON ATOMS. 